Method of making mixtures of internal olefins

Abstract

The invention provides new methods for the synthesis of isomeric mixtures of alkenes from α-olefins or mixtures of internal and terminal alkenes (i.e., predominantly α-olefins). The invention describes the process for producing an isomeric mixture of at least one internal alkene comprising contacting at least one or a mixture of alkene feedstock with a heterogeneous catalyst comprising a group IV metal oxide at a temperature and pressure conducive to positional isomerization of the double bond. The methods of the invention are particularly suitable for the preparation of isomeric mixtures of olefins suitable for use as additives in the paper making process and particularly as ASA sizing agents.

1 . A process for producing an isomeric mixture of at least one x-C n -alkene comprising contacting at least one C n -alkene feedstock with a heterogeneous catalyst system comprising a group IV metal oxide at a temperature and pressure conducive to positional isomerization of the double bond of C n -alkene feedstock, and recovering said isomeric mixture of at least one x-C n -alkene, wherein n is one or more integers selected from 8 to 40; and x defines the position of the alkene double bond in the n-carbon alkene chain wherein the average value of x is between 2 and n/2.  
   
   
       2 . The process of  claim 1 , wherein the average value of x is between about 3 and n/2.  
   
   
       3 . The process of  claim 1 , wherein the C n -alkene feedstock is one or more α-alkenes, one or more linear alkenes having a disubstituted double bond, or a combination thereof.  
   
   
       4 . The process of  claim 1 , wherein the C n -alkene feedstock is one or more linear alkenes having a disubstituted double bond.  
   
   
       5 . The process of  claim 1 , wherein the heterogeneous catalyst system comprises between 0. 1% and about 100% titanium oxide by weight.  
   
   
       6 . The process of  claim 5 , wherein the heterogeneous catalyst system comprises between 50% and about 100% titanium oxide by weight.  
   
   
       7 . The process of  claim 6 , wherein the heterogeneous catalyst system comprises between 75% and about 100% titanium oxide by weight.  
   
   
       8 . The process of  claim 1 , wherein the heterogeneous catalyst system comprises titanium oxide and at least one additional material selected from Rh, Ir, Ni, Pd, Pt, and solid acid catalysts.  
   
   
       9 . The process of  claim 8 , wherein the additional catalyst is a Pd catalyst.  
   
   
       10 . The process of  claim 1 , wherein the heterogeneous catalyst system comprises a group IV metal oxide and at least one other solid capable of providing structural support.  
   
   
       11 . The process of  claim 10 , wherein the group IV metal oxide is titanium oxide and the solid capable of providing structural support is selected from silica, alumina, carbon, diatomaceous clays, and mixtures thereof.  
   
   
       12 . The process of  claim 10 , wherein the heterogeneous support comprises between about 25% and about 95% titanium oxide and between about 75% and about 5% of a structural material selected from silica, alumina, or carbon, diatomaceous clays, and mixtures thereof.  
   
   
       13 . The process of  claim 1 , wherein the heterogeneous metal oxide comprises between about 0. 1% and about 20% of a sulfate salt or sulfuric acid by weight of the heterogeneous metal oxide.  
   
   
       14 . The process of  claim 13 , wherein the heterogeneous metal oxide comprises between about 1% and about 10% of a sulfate salt or sulfuric acid by weight of the heterogeneous metal oxide.  
   
   
       15 . The process of  claim 14 , wherein the heterogeneous metal oxide comprises between about 3% and about 7% of a sulfate salt or sulfuric acid by weight of the heterogeneous metal oxide.  
   
   
       16 . The process of  claim 1 , wherein the heterogeneous catalyst has a surface area of between about 50 and about 500 m 2 /g.  
   
   
       17 . The process of  claim 16 , wherein the heterogeneous catalyst has a surface area of between about 150 and about 300 m 2 /g.  
   
   
       18 . The process of  claim 1 , wherein the heterogeneous catalyst has a pore diameter of between about 50 Å and about 400 Å.  
   
   
       19 . The process of  claim 18 , wherein the heterogeneous catalyst has a pore diameter of between about 100 Å and about 200 Å.  
   
   
       20 . The process of  claim 1 , wherein the C n -alkene feedstock is selected from α-alkenes having between 12 and 30 carbon atoms, internal alkenes having between 12 and 30 carbon atoms, and mixtures thereof.  
   
   
       21 . The process of  claim 20 , wherein the C n -alkene feedstock is selected from 1-dodecene, 1-tetradecene, 1-hexadecene, 1-octadecene, 1-eicosene, 1-docosene, 1-tetracosene, or a mixture thereof.  
   
   
       22 . The process of  claim 20 , wherein the C n -alkene feedstock is selected from 1-tetradecene, 1-hexadecene, 1-octadecene, 1-eicosene, or a mixture thereof.  
   
   
       23 . The process of  claim 20 , wherein the C n -alkene feedstock is a mixture of 1-hexadecene and 1-octadecene.  
   
   
       24 . The process of  claim 23 , wherein the ratio of 1-hexadecene to 1-octadecene is between about 1:10 and about 10:1.  
   
   
       25 . The process of  claim 20 , wherein the C n -alkene feedstock consists essentially of 1-hexadecene or 1-octadecene.  
   
   
       26 . The process of  claim 20 , wherein the feedstock is selected from 1-dodecene, 1-tetradecene, 1-hexadecene, 1-octadecene, 1-eicosene, 1-docosene, 1-tetracosene, and internal alkenes wherein n is 12-30; and mixtures thereof.  
   
   
       27 . The process of  claim 20 , wherein the feedstock is selected from internal alkenes wherein n is 12-30.  
   
   
       28 . The process of  claim 1 , wherein the C n -alkene feedstock is contacted with the heterogeneous catalyst at a temperature of about 500° F. or less.  
   
   
       29 . The process of  claim 28 , wherein the C n -alkene feedstock is contacted with the heterogeneous catalyst at a temperature of between about 250° F. and about 400° F.  
   
   
       30 . The process of  claim 1 , wherein the C n -alkene feedstock is contacted with the heterogeneous catalyst at a pressure of less than about 100 atmospheres.  
   
   
       31 . The process of  claim 30 , wherein the C n -alkene feedstock is contacted with the heterogeneous catalyst at a pressure of between about 1 and about 75 atmospheres.  
   
   
       32 . The process of  claim 1 , wherein the C n -alkene feedstock is contacted with the heterogeneous catalyst in the absence of water.  
   
   
       33 . The process of  claim 1 , wherein the isomeric mixture of x-C n -alkenes is selected from alkene mixtures in which the average value of x is between about 3 and about 7, and n is one, two, three, or four integers of between 12 and 24.  
   
   
       34 . The process of  claim 33 , wherein at least about 40% of the occurrences of x is an integer of between 3 and about n/2.  
   
   
       35 . The process of  claim 34 , wherein at least about 80% of the occurrences of x is an integer of between 3 and about n/2.  
   
   
       36 . The process of  claim 1 , wherein the isomeric mixture of at least one x-C n -alkene comprises at least about 40% of gamma, delta, epsilon, and eta-alkene positional isomers of the x-C n -alkene mixture.  
   
   
       37 . The process of  claim 36 , wherein the isomeric mixture of at least one x-C n -alkene comprises at least about 80% of gamma, delta, epsilon, and eta alkene positional isomers of the x-C n -alkene mixture.  
   
   
       38 . The process of  claim 36 , wherein the C n -alkene is tetradecene, hexadecene, octadecene, eicosene, or a mixture thereof.  
   
   
       39 . The process of  claim 36 , wherein the C n -alkene is hexadecene, octadecene, or a mixture thereof.  
   
   
       40 . The process of  claim 1 , wherein the isomeric mixture of x-C n -alkenes is selected from alkene mixtures in which the average value of x is between about 2 and about 7, and n is one, two or three integers of between 12 and 24.  
   
   
       41 . The process of  claim 1 , wherein at least about 40% of the occurrences of x is an integer of between 1 and about 7.  
   
   
       42 . The process of  claim 41 , wherein at least about 80% of the occurrences of x is an integer of between 2 and about 6.  
   
   
       43 . The process of  claim 1 , wherein the isomeric mixture of at least one x-C n -alkene comprises at least about 40% of alpha, beta, gamma, delta, epsilon, and eta-alkene positional isomers of the x-C n -alkene mixture.  
   
   
       44 . The process of  claim 43  wherein the isomeric mixture of at least one x-C n -alkene comprises at least about 80% of beta, gamma, delta, epsilon, and eta alkene positional isomers of the x-C n -alkene mixture.  
   
   
       45 . The process of  claim 43 , wherein the C n -alkene is tetradecene, hexadecene, octadecene, eicosene, or a mixture thereof.  
   
   
       46 . The process of  claim 43 , wherein the C n -alkene is hexadecene, octadecene, or a mixture thereof.  
   
   
       47 . The process of  claim 8 , wherein the additional material selected from Rh, Ir, Ni, Pd, Pt, and solid acid catalysts initially converts the C n -alkene feedstock to an isomeric mixture of at least one z-C n -alkene, wherein n is one or more integers selected from 8 to 40; and z defines the position of the alkene double bond in the n-carbon alkene chain wherein the average value of z is between 2 and n/2.  
   
   
       48 . The process of  claim 47 , wherein the average value of z is between about 3 and less than n/2.  
   
   
       49 . The process of  claim 48 , wherein the additional material is a Pd catalyst.  
   
   
       50 . The process of  claim 49 , wherein the heterogeneous catalyst system comprising a group IV metal oxide isomerizes the double bond of the z-C n -alkene to a mixture of x-C n -alkene, wherein n is one or more integers selected from 8 to 40; and x defines the position of the alkene double bond in the n-carbon alkene chain wherein the average value of x is between 2 and n/2 or more preferably greater than 3 and less than n/2; and wherein x is greater than z.  
   
   
       51 . The process of  claim 1 , wherein the C n -alkene feedstock is contacted with the heterogeneous catalyst system in a continuous flow, fixed bed reactor.  
   
   
       52 . The process of  claim 1 , wherein the C n -alkene feedstock is contacted with the heterogeneous catalyst system in a batch reactor.  
   
   
       53 . The process of  claim 51 , wherein a flow of C n -alkene feedstock is contacted with the heterogeneous catalyst system at a rate of between about 0.1 to about 50 (kilograms C n -alkene feedstock per hour per kilogram of heterogeneous catalyst).  
   
   
       54 . The process of  claim 1 , wherein the catalyst can act as a stand alone catalyst, a pre-isomerization catalyst, or a tailing catalyst.  
   
   
       55 . The process of  claim 54 , wherein the catalyst is a tailing catalyst.  
   
   
       56 . A process for producing an isomeric mixture of at least one x-C n -alkene comprising contacting at least one z-C n -alkene feedstock with a heterogeneous catalyst system comprising a group IV metal oxide at a temperature and pressure conducive to positional isomerization of the double bond of C n -alkene feedstock, and recovering said isomeric mixture of at least one x-C n -alkene, wherein n is one or more integers selected from 8 to 40; 
 x defines the position of the alkene double bond in the n-carbon alkene chain wherein the average value of x is between 2 and n/2;    z defines the position of the alkene double bond in the C n -alkene feedstock, wherein the average value of z is between 1 and n/2; and    the average value of x is greater than the average value of z.    
   
   
       57 . The process of  claim 56 , wherein the average value of x is between about 3 and n/2.  
   
   
       58 . The process of  claim 56 , wherein the C n -alkene feedstock is one or more α-alkenes, one or more linear alkenes having a disubstituted double bond, or a combination thereof.  
   
   
       59 . The process of  claim 56 , wherein the C n -alkene feedstock is one or more linear alkenes having a disubstituted double bond.  
   
   
       60 . A process for producing an isomeric mixture of at least one x-C n -alkene comprising, 
 a) contacting the C n -alkene feedstock with an additional material selected from Rh, Ir, Ni, Pd, Pt, and solid acid catalysts to initially convert the C n -alkene feedstock to an isomeric mixture of at least one z-C n -alkene, wherein n is one or more integers selected from 8 to 40; and z defines the position of the alkene double bond in the n-carbon alkene chain wherein the average value of z is between 2 and n/2;    b) contacting the z-C n -alkene with a heterogeneous catalyst system comprising a group IV metal oxide at a temperature and pressure conducive to positional isomerization of the double bond and recovering an isomeric mixture of at least one x-C n -alkene;    wherein n is one or more integers selected from 8 to 40;    x defines the position of the alkene double bond in the n-carbon alkene chain wherein the average value of x is between 2 and n/2;    z defines the position of the alkene double bond in the C n -alkene feedstock;    the average value of z is between 1 and n/2; and    the average value of x is greater than the average value of z.